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Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
3 / 61
Basics of DFT
ELK 2011
4 / 61
Atomic units
In atomic units, all energies are in Hartree (1H= 27.2 eV) and all
distances in Bohr (1a0 = 0.529 )
To write formulas in atomic units, set e 2 = ~ = me = 1
In regular units,
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1 H = 27.2eV
1 eV = 23.06 kcal/mol
1 kcal = 4.184 kJ/mol = 503K.
Basics of DFT
ELK 2011
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Born-Oppenheimer approximation
Because of difference between proton and electron mass, can separate
wavefunction into product to an excellent approximation.
Because electronic energies are in eV and much greater than 300K,
electrons always in ground state.
Yields
Etotal = Enuc ({R }) + Eelec ({R })
where electons are in ground state.
Knowing Etotal ({R }) yields structures from minima, vibrations from
curvature, all reaction energies from well-depths, all transition states
from saddle points, etc.
Kieron (UC Irvine)
Basics of DFT
ELK 2011
6 / 61
Hamiltonian
Hamiltonian for N electrons in the presence of external potential v (r):
=T
+V
ee + V
,
H
where the kinetic and elec-elec repulsion energies are
= 1
T
2
N
X
N X
N
X
1
ee = 1
,
V
2 i=1 j6=i |ri rj |
2i ,
i=1
N
X
v (ri )
i=1
Z
|r R |
where runs over all nuclei, plus weak applied E and B fields.
Kieron (UC Irvine)
Basics of DFT
ELK 2011
7 / 61
Schrdinger equation
6N-dimensional Schrdinger equation for stationary states
+V
ee + V
} = E ,
{T
antisym
X
1
...
XZ
d 3 r2 . . . d 3 rN |(r1 , r2 2 , . . . , rN N )|2
E [] h|H|i
is a functional
Extrema of E [] are stationary states, and ground-state energy is
+V
ee + V
|i
E = minh|T
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
9 / 61
Basics of DFT
ELK 2011
10 / 61
Basics of DFT
ELK 2011
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+V
ee + V
|i
= minh|T
= min F [n] +
n
d r v (r)n(r)
where
F [n] =
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2
+V
ee |i
min h|T
d 3 r n(r) = N
are determined to
The external potential v (r) and the hamiltonian H
within an additive constant by n(r)
P. Hohenberg and W. Kohn, Phys. Rev. 136, B 864 (1964).
M. Levy, Proc. Natl. Acad. Sci. (U.S.A.) 76, 6062 (1979).
Kieron (UC Irvine)
Basics of DFT
ELK 2011
12 / 61
Kohn-Sham 1965
Define fictitious non-interacting electrons satisfying:
1
2 + vS (r) i (r) = i i (r),
2
N
X
|i (r)|2 = n(r).
i=1
d 3r
n(r0 )
+ vXC [n](r),
|r r0 |
Basics of DFT
vXC (r) =
EXC
n(r)
ELK 2011
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d 3 r |i (r)|2
>0
d r
d 3r 0
n(r) n(r0 )
|r r0 |
>0
1 XX
2 i,j
d 3r
d 3r 0
occ
EC is everything else.
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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Basics of DFT
ELK 2011
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KS potential of He atom
vS (r )
vext (r )
n(r )
1
Accurate exchange-correlation potentials and total-energy components for the
helium isoelectronic series, C. J. Umrigar and X. Gonze, Phys. Rev. A 50, 3827 (1994).
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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T
He 2.904
Be 14.67
Ne 128.9
Vext
-6.753
-33.71
-311.1
Vee TS
0.946 2.867
4.375 14.59
53.24 128.6
U
2.049
7.218
66.05
EX
-1.025
-2.674
-12.09
TC
.037
.073
.33
UC
-.079
-.169
-.72
EC
-.042
-.096
-.39
Basics of DFT
ELK 2011
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N
X
i
i=1
If some approximation is used for EXC , then energy can go below the
exact ground-state energy.
Any given formula for EXC , no matter where it came from, produces a
non-empirical scheme for all electronic systems.
The KS scheme, even with the exact functional, yields only E and
n(r) (and anything that can be deduced from them).
In principle, from HK, all properties are determined by n(r), but in
reality, we only know one really well.
Basics of DFT
ELK 2011
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=I A
S = HOMO LUMO
Basics of DFT
ELK 2011
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Spin DFT
In modern reality, everyone uses spin-density functional theory
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Basics of DFT
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DFT is
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Exact DFT tells us what we can and cannot expect our functionals to
be able to do.
vS (r) and j (r) are not real, just logical constructions. The j (r) can
be very useful interpretative tools and follow intuition, but vS (r) is
dangerous.
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
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unif
d 3 r eXC
(n(r))
Hybrid:
hyb
GGA
EXC
[n] = a(EX EXGGA ) + EXC
[n]
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Basics of DFT
ELK 2011
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Functional Soup
Good: choose one functional of each kind and stick with it (e.g.,
LDA, PBE, or PBE0).
Bad: Run several functionals, and pick best answer.
Ugly: Design your own functional with 2300 parameters.
Empirical
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Non-empirical
GGA: BLYP
Hybrid: B3LYP
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Names:
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GGA:PBE
Meta-GGA: TPSS
Hybrid: PBE0
B=B88 exchange
LYP = Lee-Yang-Parr
correlation
Basics of DFT
ELK 2011
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Functional Soup
Good: choose one functional of each kind and stick with it (e.g.,
LDA, PBE, or PBE0).
Bad: Run several functionals, and pick best answer.
Ugly: Design your own functional with 2300 parameters.
Empirical
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Non-empirical
GGA: BLYP
Hybrid: B3LYP
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Names:
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GGA:PBE
Meta-GGA: TPSS
Hybrid: PBE0
B=B88 exchange
LYP = Lee-Yang-Parr
correlation
Basics of DFT
ELK 2011
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Functional Soup
Good: choose one functional of each kind and stick with it (e.g.,
LDA, PBE, or PBE0).
Bad: Run several functionals, and pick best answer.
Ugly: Design your own functional with 2300 parameters.
Empirical
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Non-empirical
GGA: BLYP
Hybrid: B3LYP
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Names:
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GGA:PBE
Meta-GGA: TPSS
Hybrid: PBE0
B=B88 exchange
LYP = Lee-Yang-Parr
correlation
Basics of DFT
ELK 2011
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AX = 0.738
Basics of DFT
ELK 2011
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Basics of DFT
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Densities
Basics of DFT
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Easy conditions
Size-consistency:
EXC [nA + nB ] = EXC [nA ] + EXC [nB ],
where nA (r) and nB (r) do not overlap.
Uniform limit: Recover exact XC bulk jellium energy if n is constant.
Linear response of uniform gas: LDA is almost exact for linear
response to perturbation cos(q r) for q 2kF .
Lieb-Oxford bound: Magnitude of EXC cannot be greater than 2.3
EXLDA .
Basics of DFT
ELK 2011
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n HxL
nHxL
0
-1
0
x
Basics of DFT
ELK 2011
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History of GGA
Gradient expansion approximation (GEA): Expansion in density
gradients that is valid for slowly-varying gas, discussed in KS65.
Langreth-Mehl 81: First modern GGA, but cut-off in wavevector
space.
PW86: Early version of Perdew strategy, cutting off
gradient-expanded hole in real space. (Phys. Rev. B, 33)
B88: Axel Becke EXGGA , based on energy density of atoms, one
parameter (Phys. Rev. A. 38)
LYP, 88: Lee-Yang-Parr turn Colle-Salvetti orbital functional for
atoms into an EC [n] (Phys. Rev. B. 37)
PW91: Parametrization of real-space cut-off procedure
PBE, 96: A re-parametrization and simplification of PW91
RPBE, 99: Danish version, improves surface energetics
PBEsol, 08: Revised PBE for solids
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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Philosophy of GGA
If LDA is very reliable using only n(r), surely can be more accurate if
use n(r) too.
Use exact conditions to constrain construction.
Non-empirical (Perdew):
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Empirical (Becke):
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Pragmatic (Kieron):
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Basics of DFT
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PBE, 1996
Correlation:
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Exchange:
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0.804.
Performance
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Basics of DFT
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Hybrids
A hybrid functional replaces some fixed fraction of GGA exchange
with exact exchange.
First proposed by Becke
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Morphed into the infamous B3LYP, now most used functional in DFT.
The 3 in B3LYP is 3 fitted parameters, but other 2 just modify GGA.
PBE0 is the derived version, with 1/4 mixing rationalized.
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Basics of DFT
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0.1
-50%
1
-30%
2
-40%
5
-50%
10
-60%
Basics of DFT
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Applications of DFT
Tens of thousands of papers every year.
Appearing in every branch of science:
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Solid-state physics
Chemistry
Biochemistry
Geology
Astrophysics
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
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n(r) Ar e
2Ir
(r )
HOMO = I
Basics of DFT
ELK 2011
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E
N(
Basics of DFT
I, N Z
A, N > Z
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Basics of DFT
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Basics of DFT
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Basics of DFT
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Basics of DFT
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Stretched H2
Consider H2 as R :
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e.g. Yang et. al, 8 August 2008 Science 321 (5890), 792
E (R) 2E (H),
But is always a singlet, for large but finite R, have 1/2 electron of
each spin on each atom.
Single-reference wavefunction has one doubly-occupied molecular
orbital, but becomes Heitler-London wavefunction, which is
completely different.
Any single-reference theory gives spin-unpolarized H atoms that are
wrong in energy.
Symmetry dilemma: Can allow spin-symmetry to break, and get right
energetics, but then no longer a spin eigenstate.
Coulson-Fischer point is R when symmetry spontaneously breaks in
approximate treatment
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
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Z 1
EXC [n] =
0
dE
d XC =
d
Z 1
0
d UXC
[n]
D.C. Langreth and J.P. Perdew, Solid State Commun. 17, 1425 (1975).
O. Gunnarsson and B.I. Lundqvist, Phys. Rev. B 13, 4274 (1976).
Basics of DFT
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M. Fuchs, Y.-M. Niquet, X. Gonze, and K. Burke, J. Chem. Phys. 122, 094116 (2005)
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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1
4
J.P. Perdew, M. Ernzerhof, and K. Burke, J. Chem. Phys. 105, 9982 (1996).
Kieron (UC Irvine)
Basics of DFT
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Orbital dependence
There are many effects due to discrete orbitals that are missed.
Some of these effects are seriously weird, but are important to know
about.
Basics of DFT
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Basics of DFT
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EC [n] = 0
(N = 1)
Basics of DFT
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N
X
EHXC [|j |2 ]
j=1
Basics of DFT
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What do the Kohn-Sham orbitals mean? How do atoms dissociate?, J.P. Perdew, in
Density Functional Methods in Physics, edited by R.M. Dreizler and J. da Providencia
(Plenum, NY, 1985), p. 265.
Kieron (UC Irvine)
Basics of DFT
ELK 2011
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Outline
General background
DFT
Common functionals
Miscellaneous
Basics of DFT
ELK 2011
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Jacobs ladder
to DFT heaven
(or hell?)
Increasingly sophisticated
and expensive density
functional
approximations.
Z
EXC =
d 3 r f (n, n, , . . .)
Basics of DFT
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No self-interaction error
Potentials and orbital energies much better
Approximates derivative discontinuity
Stephan Kmmel and Leeor Kronik, Rev. Mod. Phys. 80, 3 (2008)
Basics of DFT
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Basics of DFT
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F
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Grimme,LW
Axel D. Becke and Erin R. Johnson J. Chem. Phys. 127, 154108 (2007)
Basics of DFT
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Excitations
Many ways to do excitations in DFT
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Ensemble DFT
SCF
min-max principle
Basics of DFT
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Short-term results
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Long-term goals
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Basics of DFT
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PBEsol
Exchange:
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Correlation
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unif
For large neutral jellium clusters, EXC = eXC
(n) V + XC (n) A + ... .
= 0.046 gives best energy (PBE had .0667).
First proposed by Armiento and Mattsson (2005), whose functional
gives almost identical lattice parameters.
Performance:
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Johansson, Lechtken, Schooss, Kappes, and Filipp Furche, Phys. Rev. A 77,
053202 (2008)
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I Perdew, Ruzsinszky, Csonka, Vydrov, Scuseria, Constantin, Zhou, and KB, Phys. Rev. Lett. 100, 136406 (2008)
Kieron (UC Irvine)
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Basics of DFT
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